JP2011128359A - Positive photosensitive resin composition, cured film using the same and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a positive photosensitive resin composition showing excellent adhesion to a substrate after curing and excellent storage stability of varnish. <P>SOLUTION: The positive photosensitive resin composition contains (a) a polymer soluble in an alkaline aqueous solution, (b) a compound which generates an acid upon irradiation with light, (c) acetic acid, and (d) a silane coupling agent having a urea bond. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition, a cured film, a pattern production method, and an electronic component, and more specifically, a heat-resistant positive photosensitive resin composition containing a heat-resistant polymer having photosensitivity. The present invention relates to a method for producing a cured film and a pattern using the same, and an electronic component.

  Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. However, in recent years, with the progress of higher integration and larger size of semiconductor elements, there is a demand for thinner and smaller sealing resin packages. Surface mounting by LOC (lead-on-chip) or solder reflow Such a system has been adopted, and a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.

  Furthermore, photosensitive polyimide having photosensitive properties imparted to the polyimide resin itself has been used, but if this is used, the pattern manufacturing process can be simplified, and complicated manufacturing processes can be shortened. A heat-resistant photoresist using a conventional photosensitive polyimide or its precursor and its application are well known. In the negative photosensitive polyimide, a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond, a soluble polyimide having a photopolymerizable olefin, an aromatic ring having a benzophenone skeleton and a nitrogen atom bonded thereto. There is a self-sensitized polyimide having an alkyl group at the ortho position.

Since the above-mentioned negative photosensitive polyimide requires an organic solvent such as N-methylpyrrolidone at the time of development, a positive photosensitive resin that can be developed with an aqueous alkaline solution has been recently proposed. In the positive type, a method in which an o-nitrobenzyl group is introduced into a polyimide precursor via an ester bond (for example, see Non-Patent Document 1), a method in which a naphthoquinonediazide compound is mixed in a soluble hydroxylimide or polyoxazole precursor (for example, , Patent Documents 1 and 2), a method of introducing naphthoquinone diazide into a soluble polyimide via an ester bond (for example, see Non-Patent Document 2), and a method in which naphthoquinone diazide is mixed into a polyimide precursor (for example, see Patent Document 3) )and so on.

  However, the above-mentioned negative photosensitive polyimide has problems in terms of function and resolution, and in some applications, yields are reduced in production. In addition, since the structure of the polymer to be used is limited in the above, the physical properties of the finally obtained film are limited, which is not suitable for multipurpose use. On the other hand, the positive photosensitive polyimide also has the same problems due to the problems associated with the absorption wavelength of the photosensitive agent as described above, and the sensitivity and resolution are low and the structure is limited.

  Also, a polybenzoxazole precursor mixed with a diazonaphthoquinone compound (for example, see Patent Document 4), or a polyamic acid with a phenol moiety introduced through an ester bond (for example, Patent Document 5). Some have a phenolic hydroxyl group introduced in place of the carboxylic acid. However, these have insufficient developability, resulting in film loss at unexposed areas and peeling of the resin from the substrate. For the purpose of improving developability and adhesion, a mixture of polyamic acids having a siloxane moiety in the polymer skeleton has been proposed (see, for example, Patent Documents 6 and 7). Storage stability deteriorates due to use. In addition, for the purpose of improving storage stability and adhesion, amine end groups sealed with a polymerizable group (for example, see Patent Documents 8 to 11) have also been proposed. As a diazoquinone compound containing a large number of aromatic rings is used, the sensitivity is low, and it is necessary to increase the amount of diazoquinone compound added. It is.

JP-A 64-60630 US Pat. No. 4,395,482 JP 52-13315 A Japanese Patent Publication No. 64-46862 JP-A-10-307393 JP-A-4-31861 Japanese Patent Laid-Open No. 4-46345 JP-A-5-197153 JP-A-9-183846 JP 2001-183835 A Japanese Patent Laid-Open No. 3-763 J. et al. Macromol. Sci. Chem. , A24, 12, 1407, 1987 Macromolecules, 23, 4796, 1990

  In recent years, photosensitive polyimide or photosensitive polybenzoxazole has been increasingly used as a semiconductor surface protective film, a rewiring layer, and an interlayer insulating film in accordance with a change in package form in a semiconductor device. Usually, these precursor compositions are coated on various substrates, exposed with actinic radiation, patterned by subsequent development with an organic solvent or an alkaline aqueous solution, and finally formed into a polyimide film or a polybenzoxazole film by high-temperature heat treatment. . However, the adhesion between the film after heat curing and the substrate is poor, and there are often cases where the fine pattern is peeled off from the substrate by the chemical treatment performed after heat curing. With respect to these adhesive properties, attempts have been made such as a method of pretreating a substrate to be used, a method of imparting adhesive properties to the base polymer itself, and a method of adding an adhesion assistant.

  Conventionally, it has been found that when a silane coupling agent, which is an adhesion assistant, is used, adhesion to a cured substrate can be obtained. In particular, a silane coupling agent having a urea bond has a high effect of improving adhesion. However, if the varnish to which the coupling agent is added is allowed to stand at room temperature for a long time, a foreign substance that may be a reaction product of a silane coupling agent having a urea bond may be generated in the pattern film.

  Foreign matter in the pattern film has a problem of poor appearance, cloudiness and irregularities are generated when a metal layer is applied on the film, and adhesion to the substrate is lowered.

  In order to solve the above-mentioned problems, the present invention has been found that by combining acetic acid, it is possible to obtain a photosensitive resin composition having no foreign matter and good stability.

（式中、ｑは１〜１０の整数、Ｒ^４及びＲ^５は各々独立に炭素数１〜５のアルキル基、ｒは０〜２である。）
７．１〜６のいずれか１項に記載のポジ型感光性樹脂組成物を硬化させたことを特徴とする硬化物。
８．１〜６のいずれか１項に記載のポジ型感光性樹脂組成物を支持基板上に塗布、乾燥して感光性樹脂膜を形成する工程と、前記塗布、乾燥工程により得られた感光性樹脂膜を露光する工程と、前記露光後の感光性樹脂膜の露光部を除去するためにアルカリ水溶液を用いて現像する工程と、及び前記現像後の感光性樹脂膜を加熱処理する工程を含むことを特徴とするパタ−ンの製造方法。
９．７に記載の硬化物が層間絶縁膜層、再配線層又は表面保護膜層として設けられていることを特徴とする電子部品。 According to the present invention, the following positive photosensitive resin composition and the like are provided.
1. (A) a polymer soluble in an alkaline aqueous solution;
(B) a compound that generates acid upon irradiation with light;
(C) acetic acid;
(D) a silane coupling compound having a urea bond;
A positive-type photosensitive resin composition comprising:
2. The component (c) is 0.1 to 5 parts by weight with respect to 100 parts by weight of the component (a),
2. The positive photosensitive resin composition according to 1, wherein the component (d) is 0.1 to 30 parts by weight with respect to 100 parts by weight of the component (a).
3. The positive photosensitive resin composition according to 1 or 2, wherein the component (a) is at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
4). The positive photosensitive resin composition according to any one of 1 to 3, wherein the component (a) is a polybenzoxazole precursor.
5). The positive photosensitive resin composition according to any one of 1 to 4, wherein the component (b) is a diazonaphthoquinone derivative.
6). The positive photosensitive resin composition according to any one of 1 to 5, wherein the component (d) is a compound represented by the following general formula.

(In the formula, q is an integer of 1 to 10, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and r is 0 to 2.)
A cured product obtained by curing the positive photosensitive resin composition according to any one of 7.1 to 6.
The positive photosensitive resin composition of any one of 8.1-6 is apply | coated and dried on a support substrate, the process which forms a photosensitive resin film, and the photosensitive obtained by the said application | coating and drying process A step of exposing the photosensitive resin film, a step of developing using an aqueous alkaline solution to remove an exposed portion of the photosensitive resin film after the exposure, and a step of heat-treating the photosensitive resin film after the development. A method for producing a pattern, comprising:
An electronic component, wherein the cured product according to 9.7 is provided as an interlayer insulating film layer, a rewiring layer, or a surface protective film layer.

  The positive photosensitive resin composition of the present invention is excellent in adhesion to a substrate after curing and excellent in storage stability of varnish.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which is one Embodiment of this invention, and has shown the 1st process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which is one Embodiment of this invention, and has shown the 2nd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which is one Embodiment of this invention, and has shown the 3rd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which is one Embodiment of this invention, and has shown the 4th process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which is one Embodiment of this invention, and has shown the 5th process. It is a schematic sectional drawing sectional drawing of the semiconductor device of another embodiment of this invention.

  Hereinafter, an embodiment of a positive photosensitive resin composition according to the present invention, a method for producing a patterned cured film using the resin composition, and an electronic component will be described in detail. Note that the present invention is not limited to the following embodiments.

[Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention is characterized by containing the following components (a) to (d).
(A) a polymer soluble in an alkaline aqueous solution,
(B) a compound that generates acid upon irradiation with light;
(C) acetic acid,
(D) Silane coupling compound having urea bond

In the present invention, by using the component (c) and the component (d) together, the component (d) is stabilized, decomposition is less likely to occur, and storage stability is improved.
Hereinafter, each component will be described.

(A) Component: Polymer Aqueous in Alkaline Aqueous Solution The component (a) used in the present invention is not particularly limited as long as it is a polymer soluble in an aqueous alkali solution.
In addition, alkaline aqueous solution is alkaline solutions, such as tetramethylammonium hydroxide (TMAH) aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution. In general, since an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by weight is used, the component (a) is preferably soluble in this aqueous solution.

One criterion that the component (a) of the present invention is soluble in an alkaline aqueous solution is as follows.
(A) A component alone or a varnish obtained by dissolving in any solvent together with the components (b), (c), and (d) described below in order is spin-coated on a substrate such as a silicon wafer. To form a coating film having a thickness of about 5 μm. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20 to 25 ° C. As a result, the component (a) is considered soluble in an alkaline aqueous solution when it can be dissolved as a uniform solution, for example, after 30 minutes.

The polymer as the component (a) has a main chain skeleton of a polyimide polymer or a polyoxazole polymer, that is, polyimide, polyamideimide, polyoxazole, polyamide, and precursors thereof (for example, polyamic acid, polyamic acid ester). It is preferable to introduce from at least one polymer compound selected from, for example, polyhydroxyamide, etc. from the viewpoint of processability and heat resistance.
From the viewpoint of solubility in alkaline aqueous solution, the polymer (a) soluble in alkaline aqueous solution is preferably a polymer having a plurality of phenolic hydroxyl groups, a plurality of carboxyl groups, or both groups.

The component (a) may be a copolymer having two or more main chain skeletons described above, or a mixture of two or more of the above polymers.
Among these, if polyimide, polyoxazole or a precursor corresponding to each is used as the component (a), the cured film obtained by using the resin composition of the present invention has higher solvent resistance, which is preferable. Therefore, as the component (a), it is preferable to use at least one selected from the group consisting of polyimide, polyoxazole, and their precursors, and selected from the group consisting of polyimide, polybenzoxazole, and their precursors. It is more preferable to use at least one selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.

The polymer and precursor that can be used as the component (a) can be synthesized, for example, by the following method.
The polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine and dehydrating and ring-closing.
The polyoxazole can be obtained, for example, by reacting dicarboxylic acid dichloride with dihydroxydiamine and dehydrating and ring-closing.
The polyamideimide can be obtained, for example, by reacting tricarboxylic acid and diamine and dehydrating and ring-closing.
The polyamide can be obtained, for example, by reacting dicarboxylic acid dichloride with diamine.
The polyamic acid (polyimide precursor) can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine.
The polyamic acid ester (polyimide precursor) can be obtained, for example, by reacting tetracarboxylic acid diester dichloride with a diamine.
The polyhydroxyamide (polyoxazole precursor) can be obtained, for example, by reacting dicarboxylic acid dichloride and dihydroxydiamine (usually those in which an amino group and a phenolic hydroxyl group are bonded to the ortho position of the aromatic ring).
Any of the above-described methods for producing a polymer can be a known method.

  Among the above-mentioned specific polymers, polyhydroxyamides (polybenzoxazole precursors) that are closed by heating to become polybenzoxazoles are excellent in heat resistance, mechanical properties, and electrical properties for current electronic components. It is being used widely as a thing. Hereinafter, examples of polyhydroxyamide will be described in detail.

（式（３）中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す）で表される構造単位を有する。
この一般式（３）で表される「ヒドロキシ基を含有するアミドユニット」は、最終的には硬化時の脱水閉環により、耐熱性、機械特性、電気特性に優れるオキサゾール体に変換される。 The polyhydroxyamide has the following general formula (3):

(In formula (3), U represents a tetravalent organic group, and V represents a divalent organic group).
The “amide unit containing a hydroxy group” represented by the general formula (3) is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure at the time of curing.

  The polyhydroxyamide that can be used in the present invention only needs to have the structural unit represented by the general formula (3). However, the solubility of the polyhydroxyamide in an alkaline aqueous solution is derived from a phenolic hydroxyl group. The “amide unit containing a hydroxy group” represented by the general formula (3) is preferably contained in a certain ratio or more.

（式（４）中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。ｊとｋは、モル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋが４０〜０モル％である。）で表されるポリヒドロキシアミドである。２つのＶは同一でも異なってもよい。
ここで、式（４）中のｊとｋのモル分率は、ｊ＝８０〜１００モル％、ｋ＝２０〜０モル％であることがより好ましい。 As such, preferably the following formula (4):

(In Formula (4), U represents a tetravalent organic group, V and W represent a divalent organic group, j and k represent a mole fraction, and the sum of j and k is 100 mol%. And j is 60 to 100 mol%, and k is 40 to 0 mol%). Two Vs may be the same or different.
Here, the molar fraction of j and k in formula (4) is more preferably j = 80 to 100 mol% and k = 20 to 0 mol%.

The polyhydroxyamide having one type of structural unit or two types of structural units represented by the general formula (4) is generally a dicarboxylic acid derivative, a hydroxy group-containing diamine, and, if necessary, a diamine other than those described above. Can be synthesized. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamines.
The dihalide derivative is preferably a dichloride derivative.

The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent.
As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.

As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess.
As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

The amount of these halogenating agents used is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, relative to 1 mol of the dicarboxylic acid derivative when reacted in a solvent. When making it react in a halogenating agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable.
The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent.
As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used.
As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used.
The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

  In the general formula (4), the tetravalent organic group represented by U is preferably a tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and tetravalent having 6 to 40 carbon atoms. The aromatic group is more preferable. As the tetravalent aromatic group, those in which all four bonding sites are present on the aromatic ring are preferable. In addition, since the tetravalent organic group represented by U is a polybenzoxazole precursor, it generally reacts with a dicarboxylic acid to form a polyamide structure with “two hydroxy groups and two amino groups. It is a residue of a diamine having two sets of structures each having an hydroxy group and an amino group located in the ortho position, each having an aromatic ring.

  Such diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane. Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-) 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Although hexafluoropropane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

  In the general formula (4), the divalent organic group represented by W is generally a “diamine residue” that forms a polyamide structure by reacting with a dicarboxylic acid, and other than the diamine that forms the U. It is a residue and is preferably a divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 And aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. In addition to these, diamines containing silicone groups include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E ( Any of these include, but are not limited to, Shin-Etsu Chemical Co., Ltd., trade name).
These compounds can be used alone or in combination of two or more.

  In the general formula (4), the divalent organic group represented by V is a dicarboxylic acid residue that reacts with diamine to form a polyamide structure, and is preferably a divalent aromatic group, preferably a carbon atom. The number is preferably 6 to 40, and a divalent aromatic group having 6 to 40 carbon atoms is more preferable from the viewpoint of heat resistance of the cured film. As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred. Further, in the case where V is a divalent organic group having an aliphatic straight chain structure having 6 to 30 carbon atoms, it is preferable in that sufficient physical properties can be obtained even if the temperature at the time of thermosetting is lowered to 280 ° C. or lower. .

（式（５）中、Ｚは炭素数１〜６の炭化水素基、式中ｎは１〜６の整数である。）で示されるジカルボン酸等が挙げられるが、これらに限定されるものではない。
これらの化合物を、単独で又は２種以上を組み合わせて使用することができる。 Such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-Cyclopentanedicarboxylic acid, having an aliphatic linear structure, malonic acid Dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, Dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutar Acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacine Acid, hexadecafluoro sebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, trideca Diacid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid, docosandioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosandioic acid , Hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and the following general formula (5):

(In formula (5), Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6 in the formula.) Absent.
These compounds can be used alone or in combination of two or more.

  The molecular weight of the component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. Here, the molecular weight is a value obtained by measurement by gel permeation chromatography (GPC) and conversion from a standard polystyrene calibration curve.

(B) Component: Compound that generates acid upon irradiation with light In the composition of the present invention, together with the aqueous polymer soluble in alkali solution used as component (a), the acid is irradiated with active light as component (b). A generated compound (hereinafter also referred to as an acid generator) is used.

  The component (b) has a function of increasing the solubility of the light irradiation part in the alkaline aqueous solution. Examples of such photoacid generators include diazonaphthoquinone derivatives, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. Among them, diazonaphthoquinone derivatives are preferable because of their high sensitivity.

The diazonaphthoquinone derivative can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound and / or an amino compound in the presence of a dehydrochlorinating agent.
Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl. Sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3 -Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-Amino-4-hydroxyphenyl) hexaph Oropuropan, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound may be blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. preferable. A preferred ratio of the dehydrochlorinating agent and o-quinonediazidesulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95 (equivalent ratio).
A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent for the above reaction, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  The blending amount of component (b) is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of component (a) in order to improve the sensitivity and resolution during exposure. It is more preferably 20 parts by weight, and further preferably 0.5 to 20 parts by weight.

Component (c): Acetic acid The amount of component (c) is preferably 0.1 to 5 parts by weight, more preferably 1 to 3 parts by weight per 100 parts by weight of component (a). .

(D) Component: Silane Coupling Compound Having Urea Bond The component (d) in the present invention may be a silane coupling compound having a urea bond (—NH—CO—NH—). Preferable examples include compounds represented by the following general formula.

（式中、ｑは１〜１０の整数、好ましくは１〜５の整数である。Ｒ^４及びＲ^５は各々独立に炭素数１〜５のアルキル基、ｒは０〜２である）

(In the formula, q is an integer of 1 to 10, preferably an integer of 1 to 5. R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and r is 0 to 2).

  Specifically, ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4 -Ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc. are mentioned. Of these, 3-ureidopropyltriethoxysilane is preferable.

  The amount of component (d) is preferably 0.1-30 parts by weight, more preferably 1-10 parts by weight, and 1-3 parts by weight with respect to 100 parts by weight of component (a). Is particularly preferred.

  In the positive photosensitive resin composition of the present invention, in addition to the components (a) to (d), (e) a crosslinking agent that can be crosslinked or polymerized by heating, (f) a silane coupling compound (however, the urea bond is ), (G) thermal acid generator, (h) dissolution accelerator, (i) dissolution inhibitor, (j) adhesion promoter, (k) surfactant or leveling agent, (l) solvent, etc. Ingredients may be blended.

(E) Component: a crosslinking agent that can be crosslinked or polymerized by heating The crosslinking agent that can be crosslinked or polymerized by heating, which is the component (e) used in the present invention, is heated after coating, exposing and developing the photosensitive resin composition. In the treatment step, the compound reacts with the polymer of component (a), that is, bridges. Alternatively, the compound itself is polymerized in the heat treatment step. Thereby, the brittleness of the film, which is a concern at curing at a relatively low temperature, for example, 200 ° C. or less, can be prevented, and the mechanical properties, chemical resistance, and flux resistance can be improved.

  The component (e) is not particularly limited except that it is a compound that is crosslinked or polymerized in the heat treatment step, but is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group, or a vinyl ether group in the molecule. A compound in which these groups are bonded to a benzene ring, or a melamine resin or urea resin in which the N-position is substituted with a methylol group and / or an alkoxymethyl group is preferable. In addition, a compound in which these groups are bonded to a benzene ring having a phenolic hydroxyl group is more preferable in that the sensitivity can be improved by increasing the dissolution rate of the exposed area during development. Among them, a compound having two or more methylol groups or alkoxymethyl groups in the molecule is more preferable in that the film can be prevented from melting when the film is cured after pattern formation, and the stability of the varnish.

  Such a compound can be represented by the following general formulas (VII) to (VII).

（式中、Ｘは単結合又は１〜４価の有機基を示し、Ｒ^１１は水素原子又は一価の有機基を示し、Ｒ^１２は一価の有機基を示し、ｎは１〜４の整数であり、ｐは１〜４の整数であり、ｑは０〜３の整数である）

(Wherein, X represents a single bond or a monovalent to tetravalent organic group, R ¹¹ represents a hydrogen atom or a monovalent organic group, R ¹² represents a monovalent organic group, n represents 1 to 4 An integer, p is an integer of 1 to 4, and q is an integer of 0 to 3)

（式中、２つのＹは各々独立に水素原子又は炭素原子数１〜１０のアルキル基、その水素原子の一部又は全部がフッ素原子で置換されたフルオロアルキル基、その水素原子の一部がヒドロキシル基で置換されたヒドロキシアルキル基、炭素原子数１〜１０のアルコキシ基であり、Ｒ^１３及びＲ^１４は一価の有機基を示し、Ｒ^１５及びＲ^１６は水素原子又は一価の有機基を示し、ｍ及びｎは各々独立に１〜３の整数であり、ｐ及びｑは各々独立に０〜４の整数である）

(In the formula, two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, and part of the hydrogen atoms being A hydroxyalkyl group substituted with a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, R ¹³ and R ¹⁴ represent a monovalent organic group, and R ¹⁵ and R ¹⁶ represent a hydrogen atom or a monovalent organic group. M and n are each independently an integer of 1 to 3, and p and q are each independently an integer of 0 to 4)

（式中、Ｒ^１７及びＲ^１８は各々独立に水素原子又は一価の有機基を示し、互いが結合することで環構造となっていてもよい。）
尚、一般式（ＶＩＩ）〜（ＶＩＶ）において、一価の有機基としては、炭素原子数１〜１０の、アルキル基、アルコキシ基、ヒドロキシアルキル基、ヒドロキシアルコキシ基、それらの水素原子の一部又は全部がハロゲン原子で置換されたものが好ましいものとして挙げられる。

(Wherein R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring structure.)
In the general formulas (VII) to (VII), the monovalent organic group includes an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, and a part of hydrogen atoms having 1 to 10 carbon atoms. Alternatively, those in which all are substituted with halogen atoms are preferred.

等が挙げられるが、これらに限定されるものではない。また、こららの化合物を、単独で又は２種以上を組み合わせて使用することができる。 As the above-mentioned crosslinking agent, for example

However, it is not limited to these. Moreover, these compounds can be used individually or in combination of 2 or more types.

  In the photosensitive resin composition of the present invention, the blending amount of the component (e) (crosslinking agent that can be crosslinked or polymerized by heating) depends on the development time, the allowable width of the unexposed area remaining film ratio, and the cured film properties. Therefore, 1 to 50 parts by weight is preferable with respect to 100 parts by weight of component (a) (base resin). On the other hand, from the viewpoint of chemical resistance and flux resistance of the cured film at 230 ° C. or lower, it is preferably 15 parts by weight or more, more preferably 20 parts by weight or more.

(F) Component: Silane coupling compound (other than (d) component)
The component (f) in the present invention is not particularly limited as long as it is a silane coupling compound other than the component (d), but among them, a silane coupling compound having a hydroxy group or a glycidyl group is preferable.
Examples of the silane coupling compound having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol , Isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, , 4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilane) Le) benzene, 1,4-bis (dipropyl hydroxy silyl) benzene, and 1,4-bis (dibutyl hydroxy silyl) benzene, include compounds represented by the following formula.

（式中、ｎは１〜１０の整数、Ｒ^１はヒドロキシ基又はグリシジル基を有する１価の有機基、Ｒ^２及びＲ^３は各々独立の炭素数１〜５のアルキル基、ｐは０〜２の整数を示す。）

(In the formula, n is an integer of 1 to 10, R ¹ is a monovalent organic group having a hydroxy group or a glycidyl group, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms, and p is 0 to 0. Indicates an integer of 2.)

Of the above-mentioned compounds, the compound represented by the above general formula is particularly preferable because of its high effect of improving adhesion.
Such silane coupling agents include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyl. Triethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycid Xylethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybuty Triethoxysilane, and the like.

In addition, a silane coupling agent containing a nitrogen atom, specifically an amino group or an amide bond, together with a hydroxy group or a glycidyl group in its structure is also preferable. As such a bis (2-hydroxymethyl) ) -3-Aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-glycidoxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) ) -3-silane coupling agent having an amino group such as aminopropyltrimethoxysilane, formula _{X- (CH 2) m -CO-} NH- (CH 2) n -Si (OR) 3 ( where, X is a hydroxyl group Or glycidyl group, m and n each independently represents an integer of 1 to 3, and R is a methyl group, an ethyl group or a propyl group. And a silane coupling agent having an amide bond such as a compound represented by (1).

  The amount of component (f) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, relative to 100 parts by weight of component (a).

Component (g): Thermal acid generator In the present invention, when a thermal acid generator is used, the polymer of component (a), for example, the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and cyclizes. This is preferable because it works efficiently as a catalyst. In addition, by using this acid heat generating agent in combination with a specific resin having a high dehydration ring closure rate at about 280 ° C. or less according to the present invention, the dehydration cyclization reaction can be further lowered, so that even after curing at low temperature The physical properties of this film are comparable to those cured at high temperatures.

The acid generated from the thermal acid generator (thermal latent acid generator) is preferably a strong acid. Specifically, for example, p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, Preference is given to perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid. These acids efficiently act as a catalyst when the polymer of component (a), for example, the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and cyclizes. In contrast, acid generators that generate hydrochloric acid, bromic acid, iodic acid, and nitric acid have weak acidity and are likely to volatilize by heating. It is considered that it hardly participates in the cyclization dehydration reaction. The above-mentioned acid is added to the photosensitive resin composition of the present invention as a thermal acid generator in the form of a salt as an onium salt or in the form of a covalent bond such as imide sulfonate.

Examples of the onium salt include diaryliodonium salts such as diphenyliodonium salt, di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salt, trialkylsulfonium salts such as trimethylsulfonium salt, dimethyl A dialkyl monoarylsulfonium salt such as a phenylsulfonium salt, a diarylmonoalkyliodonium salt such as a diphenylmethylsulfonium salt, and the like are preferable. These are preferable because the decomposition start temperature is in the range of 150 to 250 ° C., and the polybenzoxazole precursor is efficiently decomposed during the cyclization dehydration reaction at 280 ° C. or less.
In contrast, triphenylsulfonium salts are not desirable as thermal acid generators. Since triphenylsulfonium salt has high thermal stability and generally has a decomposition temperature exceeding 300 ° C., the decomposition of the polymer of component (a) at 280 ° C. or lower, such as polybenzoxazole precursor, during the cyclodehydration reaction This is because it does not occur, and is considered not to function sufficiently as a catalyst for cyclization dehydration.

  From the above points, examples of suitable onium salts for the thermal acid generator used in the present invention include aryl sulfonic acid, camphor sulfonic acid, perfluoroalkyl sulfonic acid or diaryl iodonium salt of alkyl sulfonic acid, di (alkylaryl) Examples include iodonium salts, trialkylsulfonium salts, dialkylmonoarylsulfonium salts, and diarylmonoalkyliodonium salts. These are preferable from the viewpoint of storage stability and developability.

  More specifically, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid (1% weight reduction temperature 180 ° C., 5% weight reduction temperature 185 ° C.), di (t-butylphenyl) trifluoromethanesulfonic acid Iodonium salt (1% weight loss temperature 151 ° C, 5% weight loss temperature 173 ° C), trimethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 255 ° C, 5% weight loss temperature 278 ° C), trifluoromethanesulfonic acid Dimethylphenylsulfonium salt (1% weight loss temperature 186 ° C., 5% weight loss temperature 214 ° C.), diphenylmethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 154 ° C., 5% weight loss temperature 179 ° C.), Nonafluorobutanesulfonic acid di (t-butylphenyl) iodoni Can be mentioned salts, diphenyliodonium salts of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, dimethylphenyl sulfonium salt of benzenesulfonic acid, as preferred diphenyl methyl sulfonium salts of toluenesulfonic acid and the like.

The imide sulfonate is preferably naphthoyl imide sulfonate.
On the other hand, phthalimide sulfonate is not desirable because it has poor thermal stability, so that an acid is generated before the curing reaction and deteriorates storage stability.

  Specific examples of the naphthoylimide sulfonate include 1,8-naphthoylimide trifluoromethyl sulfonate (1% weight loss temperature 189 ° C., 5% weight loss temperature 227 ° C.), 2,3-naphthoyl. Preferred examples include imidotrifluoromethylsulfonate (1% weight loss temperature 185 ° C., 5% weight loss temperature 216 ° C.).

Further, as the component (g) (thermal acid generator), as shown in the following chemical formula (7), a compound having a structure of R ¹ R ² C═N—O—SO ₂ —R (1% weight reduction) A temperature of 204 ° C., a 5% weight loss temperature of 235 ° C.) can also be used. Here, as R, for example, an aryl group such as a p-methylphenyl group and a phenyl group, an alkyl group such as a methyl group, an ethyl group and an isopropyl group, a perfluoroalkyl group such as a trifluoromethyl group and a nonafluorobutyl group Etc. Examples of R ¹ include a cyano group, and examples of R ² include a methoxyphenyl group and a phenyl group.

Further, as the component (g) (thermal acid generator), as shown in the following chemical formula (8), a compound having the structure —HN—SO ₂ —R (1% weight reduction temperature 104 ° C., 5% weight reduction) A temperature of 270 ° C. can also be used. Examples of R include alkyl groups such as a methyl group, ethyl group, and propyl group, aryl groups such as a methylphenyl group and a phenyl group, perfluoroalkyl groups such as a trifluoromethyl group and nonafluorobutyl, and the like. . Examples of the group to which —HN—SO ₂ —R is bonded include 2,2, -bis (4-hydroxyphenyl) hexafluoropropane, 2,2, -bis (4-hydroxyphenyl) propane, and di ( 4-hydroxyphenyl) ether and the like.

  Furthermore, as the component (g) (thermal acid generator), a salt formed from a strong acid other than an onium salt and a base can be used. Examples of such strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, and methanesulfone. Alkyl sulfonic acids such as acids, ethane sulfonic acids, butane sulfonic acids are preferred. As the base, for example, pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, halogenated-N-alkylpyridine and the like are preferable. More specifically, p-toluenesulfonic acid pyridine salt (1% weight loss temperature 147 ° C., 5% weight reduction temperature 190 ° C.), p-toluenesulfonic acid L-aspartic acid dibenzyl ester salt (1% weight) Decrease temperature 202 ° C, 5% weight loss temperature 218 ° C), 2,4,6-trimethylpyridine salt of p-toluenesulfonic acid, 1,4-dimethylpyridine salt of p-toluenesulfonic acid, etc., storage stability, development From the viewpoint of properties, it is preferable. These can also be decomposed during the cyclization dehydration reaction of the polymer of component (a), for example, polybenzoxazole precursor, at 280 ° C. or less, and can act as a catalyst.

  The blending amount of the component (g) (thermal acid generator) is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight based on 100 parts by weight of the component (a) (base resin). 0.5-10 weight part is further more preferable.

(H) Component: Dissolution Accelerator In the present invention, a dissolution accelerator that promotes the solubility of the base resin (a) component in an alkaline aqueous solution, for example, a compound having a phenolic hydroxyl group can be contained. When the compound having a phenolic hydroxyl group is added to the photosensitive resin composition of the present invention, the development rate using the aqueous alkaline solution increases the dissolution rate of the exposed area and increases the sensitivity. During curing, the film can be prevented from melting.

  There is no restriction | limiting in particular in the compound which has the said phenolic hydroxyl group which can be used for this invention. Examples of the low molecular weight compound having a phenolic hydroxyl group include o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, and C. , E, F and G, 4,4 ′, 4 ″ -methylidynetrisphenol, 2,6-[(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ′-[ 1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] ] Phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidinetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxy Enol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol], 4,4 ′-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2, 2 ′-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl- -Hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4 ′, 4 ″-(3- Methyl-1-propanyl-3-ylidine) trisphenol, 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidyne) tetrakisphenol, 2,4,6-tris [(3 5-dimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-tris [(3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4 , 4 '-[1- [4- [1- (4-hydroxyphenyl) -3,5-bis [(hydroxy-3-methylphenyl) methyl] phenyl] -phenyl] ethylidene] bis [2,6- Bis (hydroxy-3-methylphenyl) methyl] phenol and the like can be mentioned.

  The compounding amount of the compound having a phenolic hydroxyl group is preferably 1 to 30 parts by weight relative to 100 parts by weight of the component (a) (base resin) from the viewpoint of development time and the allowable width of the unexposed part remaining film ratio. 3 to 25 parts by weight is more preferable.

(I) Component: Dissolution inhibitor In this invention, the dissolution inhibitor which is a compound which inhibits the solubility with respect to the aqueous alkali solution of the base resin which is (a) component can be further contained. Specific examples of the dissolution inhibitor include compounds such as diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide.

  These compounds are not involved in the cyclization dehydration reaction of the polybenzoxazole precursor because the generated acid is likely to volatilize. However, these compounds effectively cause dissolution inhibition and are useful for controlling the remaining film thickness and development time. The blending amount of the dissolution inhibitor is preferably 0.01 to 50 parts by weight, preferably 0.01 to 30 parts by weight based on 100 parts by weight of the component (a) (base resin), from the viewpoint of sensitivity and allowable width at the time of development. Part is more preferable, and 0.1 to 20 parts by weight is further preferable.

(J) Component: Adhesiveness imparting agent The photosensitive resin composition of the present invention comprises an organosilane compound other than the above (d) component and (f) component, an aluminum chelate, in order to enhance the adhesion of the cured film to the substrate. An adhesion-imparting agent such as a compound can be included.
Examples of such an organic silane compound include vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane.
Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.
When using the said adhesiveness imparting agent, 0.1-30 weight part is preferable with respect to 100 weight part of (a) component (base resin), and 0.5-20 weight part is more preferable.

(K) Component: Surfactant or leveling agent The photosensitive resin composition of the present invention is suitable for preventing applicability, for example, striation (film thickness unevenness) or improving developability. Surfactants or leveling agents can be added.

  Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. “Megafax F171”, “F173”, “R-08” (above, manufactured by Dainippon Ink & Chemicals, Inc.), trade names “Florard FC430”, “FC431” (above, manufactured by Sumitomo 3M Limited), trade names “ And organosiloxane polymers KP341, KBM303, KBM403, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

(L) Component: Solvent The positive photosensitive resin composition of the present invention usually contains a solvent, and the above components are dissolved or dispersed. The solvent is not particularly limited, and γ-butyrolactone (BLO), propylene glycol monomethyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), toluene, xylene, tetrahydrofuran, alcohol and the like can be used.
Although the usage-amount of the said solvent is not restrict | limited in particular, Preferably it uses it so that it may become 100 weight part-2000 weight part with respect to (a) component.

  In the composition of the present invention, excluding the solvent (l), for example, 70% or more, 80% or more, 90% or more, or 100% by weight may consist of only the components (a) to (d). . In addition to these components, the composition of the present invention may contain substances that do not substantially impair the novel and basic characteristics of the present invention, such as the components (e) to (k) described above.

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film by this invention is demonstrated.
The method for producing a cured pattern film according to the present invention includes a photosensitive resin film forming step in which the above-described photosensitive resin composition is applied onto a support substrate and dried to form a photosensitive resin film. An exposure process for exposing the pattern; a development process for developing the exposed photosensitive resin film to obtain a pattern resin film; and a heat treatment process for obtaining a pattern cured film by heat-treating the pattern resin film.
Hereinafter, each step will be described.

(Photosensitive resin film forming process)
First, in this step, the photosensitive resin composition of the present invention is used on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride using a spinner or the like. After spin coating, it is dried using a hot plate, oven or the like. Thereby, the photosensitive resin film which is a film of the photosensitive resin composition is obtained.

(Exposure process)
Next, in the exposure step, exposure is performed by irradiating the photosensitive resin film formed as a film on the support substrate with an actinic ray such as ultraviolet ray, visible ray, or radiation via a mask.

(Development process)
In the development step, a pattern cured film is obtained by removing the exposed portion of the photosensitive resin film exposed to actinic rays with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer.

(Heat treatment process)
Next, in the heat treatment step, a cured film pattern can be formed by heat-treating the pattern obtained after development. The heating temperature is preferably 280 ° C. or lower, more preferably 120 to 280 ° C., and further preferably 160 to 250 ° C.

  The heat treatment is performed using a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, or the like. Moreover, although it can select either in air | atmosphere or inert atmosphere, such as nitrogen, since it is more preferable to perform under nitrogen, the oxidation of the photosensitive resin composition film | membrane can be prevented. Since the said heating temperature range is lower than the conventional heating temperature, the damage to a support substrate or a device can be restrained small. Therefore, by using the pattern manufacturing method of the present invention, devices can be manufactured with high yield. It also leads to energy savings in the process.

  Further, as the heat treatment of the present invention, a microwave curing device or a variable frequency microwave curing device can be used in addition to using an ordinary nitrogen-substituted oven. By using these, it is possible to effectively heat only the photosensitive resin composition film while keeping the temperature of the substrate or device at, for example, 220 ° C. or lower.

  For example, in Japanese Patent Nos. 2587148 and 3031434, dehydration and ring closure of a polyimide precursor using microwaves are studied. In US Pat. No. 5,739,915, when a polyimide precursor thin film is dehydrated and closed using microwaves, there is a method for avoiding damage to the polyimide thin film or the base material by irradiating with the frequency changed in a short period. Proposed.

  When microwaves are irradiated in pulses while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. Furthermore, when the substrate includes metal wiring like an electronic component, it is possible to prevent the occurrence of electric discharge from the metal and to protect the electronic component from destruction by irradiating the microwave in pulses while changing the frequency. This is preferable.

  In the photosensitive resin composition of the present invention, the frequency of the microwave irradiated when dehydrating and cyclizing the polymer of component (a), for example, a polybenzoxazole precursor, is in the range of 0.5 to 20 GHz. Is preferably in the range of 1 to 10 GHz, and more preferably in the range of 2 to 9 GHz.

  Although it is desirable to continuously change the frequency of the microwave to be irradiated, the irradiation is actually performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is that standing waves or metal discharges occur, and the time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  Although the output of the microwave to be irradiated varies depending on the size of the apparatus and the amount of the object to be heated, it is generally in the range of 10 to 2000 W, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 500 W. Is most preferred. If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, a rapid temperature rise tends to occur.

  As described above, the temperature at which the polymer of component (a) in the photosensitive resin composition of the present invention is dehydrated and closed by microwaves is low in order to avoid damage to the polymer thin film and substrate after the dehydrated ring closure. Is preferred. In the present invention, the temperature for dehydration and cyclization is preferably 250 ° C. or lower, more preferably 240 ° C. or lower, more preferably 230 ° C. or lower, and most preferably 220 ° C. or lower. The temperature of the substrate is measured by a known method such as infrared or GaAs thermocouple.

  The microwave irradiated when dehydrating and cyclizing the polymer of component (a) in the photosensitive resin composition of the present invention is preferably turned on / off in a pulsed manner. By irradiating the microwaves in a pulsed manner, it is preferable in that the set heating temperature can be maintained and damage to the polymer thin film and the substrate of the component (a) can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is approximately 10 seconds or less.

  The time for dehydrating and ring-closing the polymer of component (a) in the photosensitive resin composition of the present invention, such as the polybenzoxazole precursor, is the time until the dehydrating and ring-closing reaction sufficiently proceeds, but in consideration of work efficiency. Approximately 5 hours or less. The atmosphere of dehydration ring closure can be selected from the air or an inert atmosphere such as nitrogen.

  In this way, the substrate having the photosensitive resin composition of the present invention as a layer is irradiated with microwaves under the above-described conditions to dehydrate and ring the polymer of the component (a) in the photosensitive resin composition of the present invention. In this case, a polymer having no difference from the physical properties of a dehydration ring closure film at a high temperature using a thermal diffusion furnace can be obtained even by a dehydration ring closure process at a low temperature using microwaves.

[Electronic components and their manufacturing processes]
Next, as an embodiment of a method for manufacturing an electronic component having a patterned cured film of the present invention, a method for manufacturing a semiconductor device will be described with reference to the drawings.
1 to 5 are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure, and represent a series of processes from a first process to a fifth process.
1 to 5, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and on the exposed circuit element. A first conductor layer 3 is formed. A film made of polyimide resin or the like as the interlayer insulating film layer 4 is formed on the semiconductor substrate by a spin coating method or the like (first step, FIG. 1).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film layer 4 as a mask by a spin coating method, and a predetermined portion of the interlayer insulating film layer 4 is formed by a known photolithography technique. A window 6A is provided so as to be exposed (second step, FIG. 2). The interlayer insulating film layer 4 exposed to the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (third step, FIG. 3).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (fourth step, FIG. 4). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

Next, the surface protective film 8 is formed. In the example of FIGS. 1-5, this surface protective film is formed as follows. That is, the photosensitive resin composition of the present invention is applied and dried by a spin coating method, irradiated with light from a mask on which a pattern forming a window 6C is formed at a predetermined portion, and then developed with an alkaline aqueous solution to form a pattern. A resin film is formed. Thereafter, the patterned resin film is heated to form a patterned cured film of a photosensitive resin as the surface protective film layer 8 (fifth step, FIG. 5).
This surface protective film layer (patterned cured film of photosensitive resin) 8 protects the conductor layer from external stress, α rays, etc., and the obtained semiconductor device is excellent in reliability. Since this surface protective film layer has particularly high adhesion to an aluminum substrate or aluminum wiring, it is suitable to be formed on the top of such a substrate or wiring.

  In the above embodiment, the surface protective film layer 8 is formed of the positive photosensitive resin composition of the present invention, but the interlayer insulating film layer 4 and the photosensitive resin layer 5 can also be formed of the composition of the present invention.

The electronic component of this invention has the pattern cured film formed by the manufacturing method of the said pattern cured film using the photosensitive resin composition of this invention like the example of the semiconductor device mentioned above. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like.
Specifically, the pattern cured film of the present invention can be used for forming a surface protective film, an interlayer insulating film of an electronic component such as a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. The electronic component according to the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the photosensitive resin composition, and can take various structures.

FIG. 6 shows a cross-sectional structure of an example of a semiconductor device according to another embodiment. This sectional view shows a multilayer wiring structure.
An Al wiring layer 20 is formed on the interlayer insulating layer 1, an insulating layer 30 (for example, a P—SiN layer) is further formed on the Al wiring layer 20, and a surface protective film layer 40 of the element is further formed. A rewiring layer 60 is formed from the pad portion 50 of the wiring layer 20 and extends to an upper portion of the core 80 which is a connection portion with the conductive ball 70 formed of solder, gold or the like as an external connection terminal. Further, a cover coat layer 90 is formed on the surface protective film layer 40. The rewiring layer 60 is connected to the conductive ball 70 through the barrier metal 100, and a collar 110 is provided to hold the conductive ball 70. When a package having such a structure is mounted, an underfill 120 may be provided to further relieve stress.

  In this figure, the photosensitive resin composition of the present invention includes not only the interlayer insulating layer 30 and the surface protective film layer 40 but also its excellent characteristics, so that the cover coat layer 90, the core 80, the collar 110, the underfill 120, etc. Very suitable as material. Since the heat-resistant photosensitive resin cured body using the photosensitive resin composition of the present invention is excellent in adhesiveness with a metal layer, a sealant and the like and has a high stress relaxation effect, the photosensitive resin composition of the present invention A semiconductor element in which the obtained heat-resistant photosensitive resin cured product is used for a cover coat layer, a core, a collar, an underfill, etc. has extremely excellent reliability.

  The semiconductor device of the present invention as shown in FIG. 6 has a cover coat formed using the above composition, a core for rewiring, a collar for balls such as solder, an underfill used for flip chips, etc. Is not particularly limited, and can have various structures.

Synthesis example 1
[Synthesis of Polybenzoxazole Precursor (Component (a))]
A 0.2 liter flask equipped with a stirrer and a thermometer was charged with 60 g of N-methylpyrrolidone, and 13.92 g (38 mmol) of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. Added and stirred to dissolve. Subsequently, while maintaining the temperature at 0 to 5 ° C., 8.55 g (32 mmol) of dodecanedioic acid dichloride and 2.36 g (8 mmol) of diphenyl ether dicarboxylic acid dichloride were added over 10 minutes each, and then returned to room temperature for 3 hours. Stirring was continued. The solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then depressurized to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer I). ). The weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer I was 39,500, and dispersion degree was 1.9.

Synthesis example 2
[Synthesis of Polybenzoxazole Precursor (Component (a))]
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C. Thereafter, 23.9 g (120 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid dichloride.

  Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.30 g (50 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred. Dissolved. Thereafter, 9.48 g (120 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid dichloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes.

  The stirred solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain a carboxyl group-terminated polyhydroxyamide (polybenzoxazole precursor) (hereinafter, Polymer II). The weight average molecular weight of polymer II determined by GPC standard polystyrene conversion was 17,600, and the degree of dispersion was 1.6.

Synthesis example 3
[Synthesis of polyimide precursor (component (a))
In a 0.2 liter flask equipped with a stirrer and a thermometer, 10 g (32 mmol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 3.87 g (65 mmol) of isopropyl alcohol were added. Was dissolved in 45 g of N-methylpyrrolidone, a catalytic amount of 1,8-diazabicycloundecene was added, and then heated at 60 ° C. for 2 hours. Then, it stirred at room temperature (25 degreeC) for 15 hours, and esterification was performed. Thereafter, 7.61 g (64 mmol) of thionyl chloride was added under ice cooling, and the mixture was returned to room temperature and reacted for 2 hours to obtain an acid chloride solution (hereinafter referred to as acid chloride solution I).

  Next, 40 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 10.25 g (28 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After stirring and dissolving, 7.62 g (64 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., the prepared acid chloride solution I was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The reaction solution after stirring was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester (polyamide precursor) having a carboxyl group terminal (hereinafter referred to as polymer III). The weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer III was 19,400, and dispersion degree was 2.2.

(Measurement conditions of weight average molecular weight by GPC method)
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

Examples 1-4 and Comparative Examples 1-3
[Preparation of photosensitive resin composition]
The components shown in Table 1 were dissolved in a solvent in which γ-butyrolactone / propylene glycol monomethyl ether acetate was mixed at a weight ratio of 9: 1 in the blending amounts shown in Table 1 to prepare photosensitive resin compositions.
In Table 1, the number in parentheses for each component indicates the amount (parts by weight) added to 100 parts by weight of the polymer (a). The amount of the solvent used was 200 parts by weight with respect to 100 parts by weight of the polymer.

  Polymers I, II, and III in Table 1 were prepared in the synthesis examples, and B1, B2 (manufactured by AZ Electronic Materials) C1, C2, D1 (manufactured by Toray Dow Corning) were as follows. .

C1: CH ₃ COOH
C2: pyridine _{D1: H 2 NCONH (CH 2} ) 3 Si (OEt) 3

[Manufacture of patterned cured film]
The photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were each spin-coated on a silicon wafer to form a coating film having a dry film thickness of 7 to 12 μm. The obtained coating film was irradiated with a predetermined pattern on the wafer by changing the i-line irradiation amount from 100 to 1000 mJ / cm ^{2 in} increments of 10 mJ / cm ² through an interference filter using an ultrahigh pressure mercury lamp as a light source. , Exposure was performed. After exposure, the substrate is heated at 120 ° C. for 3 minutes, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) until the exposed silicon wafer is exposed, rinsed with water, and patterned resin film Respectively.

  Next, the manufactured wafer with a patterned resin film was heated at 100 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.), and further heated at 200 ° C. for 1 hour. Pattern cured films (film thickness after curing, 5 to 10 μm) were obtained.

[Evaluation]
Sensitivity Necessary to adjust the development time so that the remaining film ratio (ratio of film thickness before and after development) in the unexposed area becomes 80% in the development process of pattern cured film formation and the pattern in the exposed area opens. The minimum exposure was defined as sensitivity. The opening pattern was judged while observing with a microscope. The results are shown in Table 2. All samples of the examples showed sufficient sensitivity characteristics.

・ Storage stability (foreign matter generation)
The storage stability when the photosensitive resin composition was stored at room temperature was evaluated by the following method.
The patterned cured film was formed from the photosensitive resin composition every week after the preparation, and the obtained cured film was observed with a metallographic microscope to observe whether or not foreign matter was observed on the film surface. A case where no foreign matter was observed even after storage at room temperature for 4 weeks was judged as ◯, and a case where foreign matter was generated up to 4 weeks at room temperature was judged as x.

  As can be seen from Table 2, the cured films of the examples all have a sensitivity that is not a problem in practice, and have good room temperature storage stability. On the other hand, in Comparative Example 1 in which the component (c) was not used, the room temperature storage stability was poor. Furthermore, Comparative Examples 2 and 3 in which the component (c) was changed to C2 had poor room temperature storage stability.

  The positive photosensitive resin composition of the present invention can be used as a material for a pattern cured film that becomes a surface protective film or an interlayer insulating film of an electronic component.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film layer 5 Photosensitive resin layer 6A, 6B, 6C Window 7 Second conductor layer 8 Surface protective film layer 10 Interlayer insulating layer 20 Al wiring layer 30 Insulating layer 40 Surface Protective film layer 50 Pad portion of wiring layer 60 Rewiring layer 70 Conductive ball 80 Core 90 Cover coat layer 100 Barrier metal 110 Color 120 Underfill

Claims (9)

(A) a polymer soluble in an alkaline aqueous solution;
(B) a compound that generates acid upon irradiation with light;
(C) acetic acid;
(D) a silane coupling compound having a urea bond;
A positive-type photosensitive resin composition comprising: The component (c) is 0.1 to 5 parts by weight with respect to 100 parts by weight of the component (a),
The positive photosensitive resin composition according to claim 1, wherein the component (d) is 0.1 to 30 parts by weight with respect to 100 parts by weight of the component (a).   The positive photosensitive resin composition according to claim 1, wherein the component (a) is at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.   The positive photosensitive resin composition according to claim 1, wherein the component (a) is a polybenzoxazole precursor.   The positive photosensitive resin composition according to claim 1, wherein the component (b) is a diazonaphthoquinone derivative. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the component (d) is a compound represented by the following general formula.

(In the formula, q is an integer of 1 to 10, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and r is 0 to 2.)   A cured product obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 6.   A positive photosensitive resin composition according to any one of claims 1 to 6 is applied to a support substrate and dried to form a photosensitive resin film, and the photosensitive material obtained by the application and drying steps. A step of exposing the photosensitive resin film, a step of developing using an aqueous alkaline solution to remove an exposed portion of the photosensitive resin film after the exposure, and a step of heat-treating the photosensitive resin film after the development. A method for producing a pattern, comprising:   An electronic component, wherein the cured product according to claim 7 is provided as an interlayer insulating film layer, a rewiring layer, or a surface protective film layer.

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